Biocatalytic processes and materials for enhanced carbon utilization

ABSTRACT

The present disclosure describes biocatalytic processes for producing a product, comprising providing an aqueous stream (AS) comprising at least one fermentable substrate and a gaseous stream (GS) comprising at least one of CO 2 /H 2 , H 2 , methane, and/or CO to a fermentation zone, wherein the GS and AS stream, are optionally contacted and/or mixed; the fermentation zone comprising at least one organism capable of metabolizing an AS substrate and a GS substrate, wherein the fermentation operates at conditions to mixotrophically metabolize at least one gaseous substrate in the GS and at least one substrate in the AS, producing the product. The present disclosure also describes compositions comprising an AS, a GS, and an organism, wherein the organism or an equivalent or engineered equivalent thereof is a methanotroph or a hydrogen-metabolizing or CO-metabolizing chemolithotrophic organism, and wherein the organism is capable of mixotrophic metabolism of at least one gaseous substrate in the GS and at least one substrate in the AS. The present disclosure also describes a process wherein said fermentation operates at conditions to mixotrophically metabolize at least H 2  in the gaseous stream and glycerol and lactic acid in the aqueous stream. The present disclosure also describes a system for producing a fermentation or bio-derived product.

This application claims priority to U.S. Provisional Patent ApplicationNo. 62/297,626, filed Feb. 19, 2016, the contents of which areincorporated herein by reference.

TECHNICAL FIELD

The present disclosure relates to biocatalytic processes, materials, andsystems. In particular, the present disclosure relates to biocatalyticprocesses for producing a product which comprise providing an aqueousstream comprising more than one metabolizable substrate and/or anaqueous stream and a gaseous stream, or derivatives thereof, to afermentation zone and simultaneously fermenting at least one substratein the aqueous stream and at least one substrate in the gaseous streamand/or simultaneously fermenting more than one substrate in the aqueousstream.

BACKGROUND

The production of chemicals (e.g., ethanol) from biomass feedstocks isof commercial interest. For example, ethanol is generally produced usingconventional fermentation processes that convert the starch inplant-based feedstocks into ethanol. However, conventional fermentationprocesses may only be able to convert limited concentrations of starchin these feedstocks or produce by-products of low value, and thus thespent fermentation stream may include fermentable starch and othermaterials as fermentation by-products. Described herein, arebiocatalytic processes and systems to enhance carbon utilization inproducing biomass-derived products, for example by use of fermentationby-products as feedstock for further fermentation.

In order to improve the economics of ethanol production, companies arelooking at routes to upgrade lower valuable byproduct streams intohigher value products. The spent fermentation stream (thin stillage),which is produced after the fermentation broth is treated to remove theundissolved solids and the ethanol, is typically concentrated to form acondensed corn distiller solubles (CDS) stream that is blended with thepreviously recovered solids to form a distiller dried grains andsolubles (DDGS) product and is sold as animal feed. The DDGS product isa relatively low value product and there is interest in separatinghigher value components to increase the overall value of the system. Thethin stillage stream contains potentially fermentable components thatcould be upgraded to more valuable products. A typical composition ofthin stillage stream is shown in Table 1.

TABLE 1 A typical composition of thin stillage from cellulosic biomasscompositional analysis (average of two batches). Cellulosic biomasscompositional analysis Dry matter (g/L) 7.7 Glucose (g/L) 0.9 Glucan(oligosaccharide, g/L) 12.4 Xylose (g/L) 0.7 Xylan (oligosaccharide,g/L) 3.7 Arabinose (g/L) 0.4 Arabinan (oligosaccharide, g/L) 0.5 Lacticacid (g/L) 16.8 Glycerol (g/L) 14.4 Acetic acid (g/L) 0.3 Butanediol(g/L) 1.9 Ethanol (g/L) 0.6 (Kim, et. al Bioresource Technology 99(2008) 5165-5176)

For a typical 50 million gallons per year (149 metric kilotonnes peryear) ethanol plant, over 70 metric kilotonnes on a dry weight basis ofthin stillage are produced a year, which includes almost 17 metrickilotonnes per year of glycerol and 19.5 metric kilotonnes per year oflactic acid. In addition to the thin stillage stream, a 50 milliongallon per year ethanol plant also produces 150 metric kilotonnes peryear of carbon dioxide off-gas, which is typically emitted to theatmosphere.

Glycerol is readily fermentable by a number of organisms, including E.coli (Gonzalez, et al., Biotechnology Letters, 2010, vol. 32, issue 3,pp 405-411) and Clostridium pasteurianum (Ahn, et al., BioresourceTechnology, 2011, vol. 102, issue 7, pp 4934-4937]. These organisms maybe used in systems that ferment glycerol in the thin stillage stream (orthe concentrated distiller solubles produced from the thin stillage) tohigher value products. Since fermentation processes co-produce carbondioxide along with the desired products, the typical maximum yield of aproduct from glycerol is less than 50% (0.5 metric tonnes of product permetric tonne of available glycerol) with equal amounts of carbon dioxidealso formed in the fermentation. For a 50 million gallon per yearethanol plant, this means that the maximum production capacity for adesired product Is less than 8 metric kilotonnes per year.

Fast et al. (Current Opinion in Biotechnology, 2015, 33:60-72) utilizeacetogenic anaerobic non-photosynthetic organisms that contain aWood-Ljungdahl pathway, such as Clostridium sp., to increase the yieldof products via mixotrophic fermentations by co-fermentation withcarbohydrates and gaseous feed (e.g., CO₂/H₂, or CO). Yield increasesbased on carbohydrate feeds of 2-35% are demonstrated. Clostridium sp.are shown to produce a number of potential products including lacticacid.

In another example, Shi et al. (Journal of Fermentation andBioengineering, Vol 84, No. 6, 579-587, 1997) demonstrate thatCupriavidus necator is capable of producing of poly(β-hydroxybutyricacid) (PHB) and biomass from several acidic feedstocks, includingacetic, lactic, and butyrate acids.

In another example (Karst et al., Journal of General Microbiology, 1984,130, p. 1987-1994) an aerobic chemolithoautotrophic organism, such asCupriavidus necator, is capable of mixotrophic growth with CO₂/H₂ andsuccinic acid to give production of poly(β-hydroxybutyric acid) (PHB)and biomass.

Furthermore, filamentous fungi strains, such as N. intermedia, may beused for fermentation with wheat-based thin stillage in the industrialprocess of ethanol production (Ferreira et al., Energies, 2014, 7, p.3872). N. intermedia cultivation may also be utilized to obtainfood-grade biomass as a secondary product.

SUMMARY

In one or more embodiments, the present disclosure describes abiocatalytic process for producing a product, comprising: providing anaqueous stream (AS), and/or derivative thereof, comprising at least onefermentable substrate to a fermentation zone; providing a gaseous stream(GS) comprising at least one of H₂, CO₂/H₂, methane, and/or CO to thefermentation zone, wherein the GS and AS stream are optionally contactedand/or mixed; the fermentation zone comprising at least one organismcapable of metabolizing an AS substrate and a GS substrate, wherein thefermentation operates at conditions to mixotrophically metabolize atleast one gaseous substrate in the GS and at least one substrate in theAS; and forming at least one product via the fermentation.

In one or more embodiments, the present disclosure describes acomposition comprising an AS, a GS, and an organism, wherein theorganism or an equivalent or engineered equivalent thereof is amethanotroph or a hydrogen-metabolizing or CO-metabolizingchemolithotrophic organism, and wherein the organism is capable ofmixotrophic metabolism of at least one gaseous substrate in the GS andat least one substrate in the AS.

In one or more embodiments, the present disclosure describes a systemfor producing a fermentation or bio-derived product, comprising a memberto provide an AS or derivative thereof to a fermentation zone; a memberto provide a GS or derivative thereof to a fermentation zone; afermentation zone, the fermentation zone comprising at least oneorganism capable of mixotrophic metabolism of an AS substrate and a GSsubstrate, wherein the fermentation operates at conditions tosimultaneously ferment at least one gaseous substrate in the GS and atleast one substrate present in the AS; one of more fermentation zonecontrol members, to control the conditions for fermenting; and a zonefor treating the product.

In one or more embodiments, the present disclosure describes abiocatalytic process for producing a product, comprising: providing anaqueous stream (AS) and/or derivative thereof having at least onefermentable substrate to a fermentation zone; providing a gaseous stream(GS) comprising at least one of H₂, CO₂/H₂, methane, and CO to thefermentation zone, the fermentation zone comprising at least oneorganism capable of metabolizing at least one substance in the ASsubstrate; wherein the AS comprises (1) at least one polyol suchglycerol, carbohydrates, or oligomers of carbohydrate, and (2) acarboxylic acid such as acetic acid, lactic acid, succinic acid orbutyric acid; and wherein the organism is capable of metabolizing atleast one substance in the GS.

In one or more embodiments, the present disclosure describes abiocatalytic process for producing a product, comprising: providing anaqueous stream (AS) and/or derivative thereof having at least glyceroland lactic acid to a fermentation zone; providing a gaseous stream (GS)comprising H₂ or optional CO₂/H₂, to the fermentation zone, thefermentation zone comprising at least one organism capable ofmetabolizing glycerol and lactic acid and wherein the organism iscapable of metabolizing at least one substance in the GS.

In one or more embodiments, the present disclosure describes abiocatalytic process for producing a product, comprising: providing anaqueous stream (AS) and/or derivative thereof having at least glyceroland lactic acid to a fermentation zone; providing a gaseous stream (GS)comprising H₂ or optional CO₂/H₂, to the fermentation zone, thefermentation zone comprising at least one Cupriavidus necator organismcapable of metabolizing glycerol and lactic acid and wherein theorganism is capable of metabolizing at least one substance in the GS.

In one or more embodiments, the present disclosure describes abiocatalytic process for producing a product, comprising: providing anaqueous stream (AS) from the spent fermentation broth and/or derivativethereof having at least one fermentable substrate to a fermentationzone; providing a gaseous stream (GS) comprising H₂ or optional CO₂/H₂,to the fermentation zone, the fermentation zone comprising at least oneorganism capable of metabolizing glycerol and lactic acid and whereinthe organism is capable of metabolizing at least one substance in theGS.

In one or more embodiments, providing a gaseous stream (GS) is optional.In some embodiments the present disclosure describes a biocatalyticprocess for producing a product, comprising providing an aqueous stream(AS), and/or derivative thereof, comprising (1) at least one polyol suchglycerol, carbohydrates, or oligomers of carbohydrate, and (2) acarboxylic acid such as acetic acid, lactic acid, succinic acid orbutyric acid; the fermentation zone comprising at least one organismcapable of simultaneously metabolizing at least one of the polyols andat least one of the carboxylic acids, wherein the fermentation operatesat conditions to metabolize at least one of the polyols and at least oneof the carboxylic acids in the AS; and forming at least one product viathe fermentation.

In one or more embodiments, the present disclosure describes acomposition comprising an AS and an organism, wherein the organism or anequivalent or engineered equivalent thereof is a capable of simultaneousmetabolism of (1) at least one polyol such glycerol, carbohydrates, oroligomers of carbohydrate, and (2) a carboxylic acid such as aceticacid, lactic acid, succinic acid or butyric acid in the AS.

In one or more embodiments, the present disclosure describes a systemfor producing a fermentation or bio-derived product, comprising a memberto provide an AS containing (1) at least one polyol such glycerol,carbohydrates, or oligomers of carbohydrate, and (2) a carboxylic acidsuch as acetic acid, lactic acid, succinic acid or butyric acid orderivative thereof to a fermentation zone; a fermentation zone, thefermentation zone comprising at least one organism capable ofmixotrophic metabolism of (1) at least one polyol such glycerol,carbohydrates, or oligomers of carbohydrate, and (2) a carboxylic acidsuch as acetic acid, lactic acid, succinic acid or butyric acid an ASsubstrate, wherein the fermentation operates at conditions tosimultaneously ferment (1) at least one polyol such glycerol,carbohydrates, or oligomers of carbohydrate, and (2) a carboxylic acidsuch as acetic acid, lactic acid, succinic acid or butyric acid presentin the AS; one of more fermentation zone control members, to control theconditions for fermenting; and a zone for treating the product.

In one or more embodiments, the present disclosure describes abiocatalytic process for producing a product, comprising: providing anaqueous stream (AS) and/or derivative thereof having (1) at least onepolyol such glycerol, carbohydrates, or oligomers of carbohydrate, and(2) a carboxylic acid such as acetic acid, lactic acid, succinic acid orbutyric acid to a fermentation zone; the fermentation zone comprising atleast one organism capable of metabolizing (1) at least one polyol suchglycerol, carbohydrates, or oligomers of carbohydrate, and (2) acarboxylic acid such as acetic acid, lactic acid, succinic acid orbutyric acid in the AS substrate.

In one or more embodiments, the present disclosure describes abiocatalytic process for producing a product, comprising: providing anaqueous stream (AS) and/or derivative thereof having (1) glycerol, and(2) a, lactic acid, to a fermentation zone; the fermentation zonecomprising at least one organism capable of metabolizing glycerol andlactic acid.

In one or more embodiments, the present disclosure describes abiocatalytic process for producing a product, comprising: providing anaqueous stream (AS) and/or derivative thereof having (1) glycerol, and(2) lactic acid, to a fermentation zone; the fermentation zonecomprising at least one Cupriavidus necator organism capable ofmetabolizing glycerol and lactic acid.

DESCRIPTION OF DRAWINGS

The descriptions below are provided by way of explanation. Thedisclosures of the figures are not limited to the descriptions below.

FIG. 1 is a schematic of providing corn biomass as feedstock to afermentation zone and producing a CO₂ stream, an aqueous stream, and anethanol stream.

FIG. 2 is a schematic of providing a gaseous stream and an aqueousstream to a fermentation zone and producing a product and, optionally,CO₂ by mixotrophic fermentation.

FIG. 3A is a schematic of providing corn biomass as feedstock to a firstfermentation zone, producing a CO₂ stream, an aqueous stream, and anethanol stream, wherein the aqueous stream, is subsequently provided toa second fermentation zone, producing a product and CO₂ by fermentation.

FIG. 3B is a schematic of providing corn biomass as feedstock to a firstfermentation zone, producing a CO₂ stream, an aqueous stream, and anethanol stream, wherein the aqueous stream, and an H₂ stream aresubsequently provided to a second fermentation zone, producing a productand, optionally, CO₂ by mixotrophic fermentation.

FIG. 3C is a schematic of providing corn biomass as feedstock to a firstfermentation zone, producing a CO₂ stream, an aqueous stream, and anethanol stream, wherein the CO₂ stream, the aqueous stream, and an H₂stream are subsequently provided to a second fermentation zone,producing a product and, optionally, CO₂ by mixotrophic fermentation.

FIG. 4 is a schematic of (1) providing corn biomass as feedstock to afirst fermentation zone, producing a CO₂ stream, an aqueous stream, andan ethanol stream, (2) providing water and a natural gas stream to asteam methane reformation (SMR) and water gas shift (WGS) zone,producing a stream comprising CO₂ and/or H₂, (3) providing the CO₂stream, the aqueous stream, the CO₂/H₂ stream, and an H₂ stream to asecond fermentation zone, producing a product and, optionally, CO₂ bymixotrophic fermentation.

FIG. 5 is a schematic of a process wherein (1) combustion of natural gasin a combined heat and power (CHP) unit generates power driving anelectrolytic cell and generates heat driving a boiler producing highpressure steam which drives a steam turbine producing electric powerdriving an electrolytic cell, the electrolytic cell producing H₂ bywater electrolysis for use in a mixotrophic fermentation process similarto that shown in FIG. 4 and described above, (2) CO₂ and/or H₂ for usein a mixotrophic fermentation process similar to that shown in FIG. 4and described above are derived from natural gas by a steam methanereformation (SMR) process, optionally comprising a water gas shift (WGS)process; (3) a product and, optionally, CO₂ are produced by mixotrophicfermentation in a process similar to that shown in FIG. 4 and describedabove.

FIG. 6 is a schematic of a process wherein (1) CO₂ and/or H₂ for use ina mixotrophic fermentation process similar to that shown in FIG. 4 anddescribed above are derived from natural gas by a steam methanereformation (SMR) process, optionally comprising a water gas shift (WGS)process; (2) natural gas or syngas recovered from the WGS process may beused to power a gas turbine producing electric power, driving anelectrolytic cell, the electrolytic cell producing H₂ by waterelectrolysis; (3) heat produced by the gas turbine may be used to drivea boiler producing high pressure steam driving a steam turbine producingelectric power driving an electrolytic cell, the electrolytic cellproducing H₂ by water electrolysis; (4) H₂ for use in a mixotrophicfermentation process similar to that shown in FIG. 4 and described aboveis produced by water electrolysis; (5) a product and, optionally, CO₂are produced in a mixotrophic fermentation process similar to that shownin FIG. 4 and described above.

FIG. 7 is a schematic of a process (1) providing corn biomass asfeedstock to a first fermentation zone, producing a CO₂ stream, anaqueous stream, and an ethanol stream; (2) wherein at least some of theCO₂ stream, the aqueous stream, and an H₂ stream are subsequentlyprovided to a second fermentation zone, producing a product and,optionally, CO₂ by mixotrophic fermentation; (3) wherein broth bleedfrom the second fermentation zone is treated by biomass removal and theresulting biomass-free broth is provided to the first fermentation zone.

DETAILED DESCRIPTION

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the invention, as claimed.

The disclosures herein include biocatalytic processes, biocatalysts,fermentation or bio-derived products, compositions comprising productsproduced by biocatalytic processes, compositions comprising fermentationor bio-derived products, compositions comprising biocatalysts forbiocatalytic processes, systems for producing fermentation orbio-derived products, and organisms for use in biocatalytic processes.

In some embodiments, the biocatalytic processes disclosed herein mayallow improved carbon utilization by using as feedstock for furtherfermentation the co-products of a first biomass fermentation process,for example the co-products of a corn fermentation process, such as theco-products of a process producing bio-ethanol from corn feedstock. Insome embodiments, the biocatalytic processes disclosed herein consumeco-products of a first biomass fermentation process and upgrade thoseco-products to products of greater value. In some embodiments, theco-products of a first biomass fermentation process that are of interestas feedstocks for biocatalytic processes disclosed herein include, butare not limited to, CO₂ off-gas and fermentable constituents ofstillage.

The present disclosure relates in part to biocatalytic processes forproducing a product which comprise providing an aqueous stream (AS) anda gaseous stream (GS), or derivatives thereof, to a fermentation zoneand mixotrophically metabolizing at least one substrate in the aqueousstream and at least one substrate in the gaseous stream. In someembodiments, the AS and GS are mixed prior to being provided to thefermentation zone. In some embodiments, the AS and GS are mixed in thefermentation zone, initially, regularly, or continually.

The present disclosure relates in part to biocatalytic processes forproducing a product which comprise providing an aqueous stream (AS)comprising (1) at least one polyol such glycerol, carbohydrates, oroligomers of carbohydrate, and (2) a carboxylic acid such as aceticacid, lactic acid, succinic add or butyric acid, to a fermentation zoneand simultaneously metabolizing (1) at least one polyol such glycerol,carbohydrates, or oligomers of carbohydrate, and (2) a carboxylic acidsuch as acetic acid, lactic acid, succinic acid or butyric acid.

In some embodiments, the aqueous stream comprises at least one of aspent fermentation stream, stillage from a bio-ethanol productionprocess, thin stillage stream from a bio-ethanol production process,concentrated corn distiller soluble (CDS), whole stillage stream from abio-ethanol production process, glycerol, carbohydrates, oligomers ofcarbohydrate, protein, carboxylic acid, acetic acid, lactic acid, or anaqueous stream derived thereof.

As used herein, “spent fermentation stream” means the remainder of afermentation process after removal of the product, including but notlimited to fermentation by-products and unreacted feedstock.

As used herein, “whole stillage” means the liquid and solid remaindersof a fermentation process after removal of the product.

As used herein, “thin stillage” means the liquid remainder of afermentation process after removal of the product.

As used herein, “condensed corn distiller soluble” (CDS) meansconcentrated thin stillage after removal of at least a portion of thewater. Herein, thin stillage shall include CDS.

As used herein, “bio-ethanol” means ethanol derived from biomassfeedstock.

In at least one embodiment, the AS is obtained from a milled ethanolproduction process, for example a corn or wheat milled ethanolproduction process.

In some embodiments, the AS comprises compounds selected from organicacids, fatty acids, polyols, glycerol, carbohydrates, and oligomers ofcarbohydrate, peptides, polypeptides, betaines, carbohydrates, vitamins,and enzymes. For example, the AS can comprise organic acids such assuccinic acid, lactic acid, acetic acid, citric acid, fumaric acid,folic acid, and phytic acid. For example, the AS can comprise fattyacids such as saturated, monounsaturated, and polyunsaturated fattyacids. For example, the AS can comprise fatty acids such as lauric acid,myristic acid, palmitic acid, stearic acid, oleic acid, palmitoleicacid, vaccenic acid, myristoleic acid, erucic acid, linoleic acid,linolenic acid, arachidonic acid, eicopentanoic acid, docosahexanoicacid, as well as fatty acids having a longer or shorter carbon chain, orgreater or fewer carbon bonds than those listed here, and/or doublebonds arranged in a cis or trans configuration. For example, the AS cancomprise carbohydrates such as monosaccharides, disaccharides,oligosaccharides, polysaccharides, each of which can include sugaralcohols as their entire structure or as a portion of their structure.

In at least one embodiment, the AS comprises (1) at least one glycerol,carbohydrates, or oligomers of carbohydrate, and (2) a carboxylic acid.For example, the carboxylic acid may be selected from the groupconsisting of a fatty acid, lactic acid, and acetic acid.

In at least one embodiment, the AS comprises (1) at least one glycerol,and (2) lactic acid.

In at least one embodiment the AS is derived from a bioethanol process.

In some embodiments of biocatalytic processes as herein described, afermentation broth bleed stream means a portion of the fermentationbroth that is diverted from the fermentation zone, wherein components ofthe bleed stream may be optionally added back to the fermentation broth.

In some embodiments of biocatalytic processes as herein described, afermentation broth bleed stream is removed from the fermentation zone,treated to remove biomass, and the resulting biomass-free broth isprovided to the fermentation zone, recycling the broth bleed stream. Inat least one embodiment, recycling of broth bleed stream allows improvedutilization of the feedstock. Recycling of broth bleed stream aspresently described can allow improved carbon utilization in biomassfermentation systems by recovery of fermentable constituents of thinstillage without need for an evaporation step.

In some embodiments, the gaseous stream comprises H₂. In someembodiments, the gaseous stream comprises syngas. In some embodiments,the gaseous stream comprises CO₂/H₂, H₂ and/or CO. In some embodiments,the gaseous stream comprises CO₂ and/or H₂, either or both of which maybe obtained from a steam methane reformation (SMR) process, which mayoptionally further comprise a water gas shift (WGS) process.

In some embodiments, the gaseous stream comprises CO₂ and/or H₂ and inthe fermentation zone the GS has a CO₂:H₂ molar ratio ranging from 0 to0.35 mol CO₂/mol H₂. In another embodiment the GS has a CO₂:H₂ molarratio ranging from 0.15 to 0.25 mol CO₂/mol H₂. In one embodiment pureH₂ may be fed and the only source of CO₂ may be from the AS, e.g. frommetabolism of thin stillage. In another embodiment the GS may be low inH₂.

In some embodiments, the gaseous stream comprises natural gas. In someembodiments, the GS is derived from natural gas, for example natural gaswhich may be combusted in at least one combined heat and power (CHP)unit to generate power. In at least one embodiment, the power generatedin the CHP unit is used for H₂ production via water electrolysis. In atleast one embodiment, the H₂ produced by water electrolysis is used infermentation processes described herein. In at least one embodiment, theCHP unit generates steam, which may be used to drive a turbo generatorfor generating electric power. The electric power generated may beexported, exported for use in biocatalytic processes described herein,exported for use in bio-ethanol production, and/or provide for H₂ and O₂production, thereby producing H₂ for use in fermentation processesdescribed herein. In at least one embodiment the generated powerprovides for H₂ production via water electrolysis, thereby producing H₂and O₂. In at least one embodiment H₂ thus produced is used inbiocatalytic processes as described herein. In at least one embodimentO₂ thus produced is used in biocatalytic processes as described herein.

In some embodiments, at least a portion of the gaseous stream isprovided to a gas combustion turbo-generator to generate power. In oneembodiment, the power thus produced provides for H₂ production via waterelectrolysis, thereby producing H₂ and O₂. In at least one embodiment H₂thus produced is used in biocatalytic processes as described herein. Inat least one embodiment O₂ thus produced is used in biocatalyticprocesses as described herein.

In some embodiments, at least a portion of the gaseous stream drives anon-combusting turbo generator to generate power. In one embodiment thepower thus produced provides for H₂ production via water electrolysis,thereby producing H₂ and O₂. In at least one embodiment H₂ thus producedis used in biocatalytic processes as described herein. In at least oneembodiment O₂ thus produced is used in biocatalytic processes asdescribed herein.

In some embodiments, at least a portion of the gaseous stream isprovided to a steam methane reformation (SMR) process for producingsyngas. In at least one embodiment, at least a portion of the syngasthus produced is provided to a gas turbo-generator to generate power. Insome embodiments, at least a portion of the gaseous stream is providedto a steam methane reformation (SMR) process for producing CO₂, H₂and/or CO. In at least one embodiment, at least a portion of the CO₂, H₂and/or CO thus produced is provided to a gas turbogenerator to generatepower. In one embodiment the power thus produced provides for H₂production via water electrolysis, thereby producing H₂ and O₂. In atleast one embodiment H₂ thus produced is used in biocatalytic processesas described herein. In at least one embodiment O₂ thus produced is usedin biocatalytic processes as described herein.

In the biocatalytic processes described herein, the fermentation zonecomprises at least one organism capable of metabolizing an AS substrateand a GS substrate and the fermentation operates at conditions tomixotrophically metabolize at least one gaseous substrate in the GS andat least one gaseous substrate in the AS. As used herein,“mixotrophically metabolize” means metabolize different sources ofenergy and carbon. Thus, the at least one organism is an organism thatcan utilize substrates from diverse sources, for example an organismcapable of metabolizing at least one substrate from the AS and at leastone substrate from the GS at the fermentation zone conditions.

In some embodiments, the conditions to mixotrophically metabolize atleast one gaseous substrate in the GS and at least one substrate presentin the AS are a pH from about 6 to about 8, a temperature from about 30°C. to about 40° C., and a pressure of above 1 atm absolute. In someembodiments, the fermentation zone pressure is above 1 atm absolute, forexample above 2 atm absolute, such as above 2.5 atm absolute. In someembodiments, the fermentation zone pressure is from about 1.5 to about10 atm absolute, such as from about 1.5 to about 8 atm absolute, such asfrom about 1.5 to about 5 atm absolute, such as from about 2.5 to about4 atm absolute.

In some embodiments, the conditions to metabolize at least one polyolsuch glycerol, carbohydrates, or oligomers of carbohydrate, and (2) atleast one carboxylic acid such as acetic acid, lactic acid, succinicacid or butyric acid present in the AS are a pH from about 6 to about 8and a temperature from about 30° C. to about 40° C.

In some embodiments, the fermentation process is aerobic ormicroaerobic.

In some embodiments, the biocatalytic processes described hereincomprise the use of biocatalysts. The term “biocatalyst,” as usedherein, refers to an isolated or purified enzyme that is in solution orimmobilized on a solid substrate, an extracellular enzyme, an enzymepresent in a cell lysate, an enzyme produced in situ by a host cell thatperforms a single chemical transformation of an organic molecule, or awhole cell that catalyzes a series of sequential transformations of oneor more organic molecules. In some embodiments, isolated orextracellular enzymes are used as biocatalysts. In some embodiments,whole cells are used as the biocatalyst. In some embodiments, bothisolated or extracellular and whole cells are used as biocatalysts. Theisolated or purified enzyme may be purchased from commercial sources, orpurified from a host cell that expresses the enzyme either naturally, ornon-naturally. The host cell may be naturally occurring or recombinant,e.g., an engineered cell. The host cell may be a prokaryote, such as abacterium or archaeon, or a eukaryote, such as a fungus (e.g., yeast) oran animal cell (e.g., a mammalian cell). The host cell may express andsecrete the enzyme, which is capable of catalyzing a particularreaction, e.g., hydrolysis.

In some embodiments, the biocatalytic processes described hereincomprise the use of microorganisms, for example naturally occurringmicroorganisms and recombinant microorganisms, e.g., engineeredmicroorganisms. In some embodiments, the organism comprises at least oneof (1) a genetic alteration, (2) a chemical alteration, and (3) anon-naturally occurring alteration.

In some embodiments, the organism or an equivalent or engineeredequivalent thereof is a methanotroph, a hydrogen-metabolizingchemolithotrophic organism, or a CO-metabolizing chemolithotrophicorganism.

In some embodiments, the organism or an equivalent or engineeredequivalent is capable of metabolizing glycerol.

In some embodiments, the organism or an equivalent or engineeredequivalent is capable of metabolizing one or more carboxylic acids suchas acetic, lactic, or butyric acids.

In some embodiments, the organism is able to metabolize both glyceroland one or more carboxylic acids such as acetic, lactic, or butyricacid.

In some embodiments, the organism is able to metabolize both glyceroland lactic acid.

In some embodiments, the organism is a methanotroph, ahydrogen-metabolizing chemolithotrophic organism, or a CO-metabolizingchemolithotrophic organism that is able to metabolize both glycerol andlactic acid.

The host cell may be a prokaryote, such as a bacterium or archaeon, or aeukaryote, such as a fungus (e.g., yeast) or an animal cell (e.g., amammalian cell). The host cell may express and secrete the enzyme, whichis capable of catalyzing a particular reaction, e.g., hydrolysis. Thehost cell can contain additional enzymatic pathways that catalyzedifferent reactions. The host cell can contain multiple enzymaticpathways active in the biocatalytic processes described herein.

In some embodiments, the host microorganism is a prokaryote. Forexample, the prokaryote can be a bacterium from the genus Clostridia,such as Clostridium ljungdahlii, Clostridium autoethanogenum, orClostridium kluyveri; from the genus Cupriavidus, such as Cupriavidusnecator (also known as Ralstonia eutropha) or Cupriavidus metallidurans;or a bacterium able to metabolize the same substrates as Cupriavidusnecator. In some embodiments, the host microorganism is a methanotroph.Such prokaryotes also can be a source of genes to construct recombinanthost cells that can be used in biocatalytic processes described herein.

In at least one embodiment, the organism is Cupriavidus necator orclostridium, or an equivalent, or engineered equivalent thereof. In someembodiments, the host microorganism is a eukaryote.

In some embodiments, the host microorganism is a chemolithotrophic host.In at least one embodiment, the host organism can be ahydrogen-metabolizing chemolithotrophic organism. For example, the hostorganism can be from the genus Hydrogenobacter, such as Hydrogenobacterthermophiles or an equivalent or engineered equivalent thereof; or fromthe genus Hydrogenophaga, such as Hydrogenophaga pseudoflava or anequivalent or engineered equivalent thereof. For example, the organismcan be Aquaspirillum autotrophicum or an equivalent or engineeredequivalent thereof. In at least one embodiment, the organism can be aCO-metabolizing chemolithotrophic organism.

In some embodiments, the hydrogen-metabolizing chemolithotrophicorganism is capable of metabolizing carbon dioxide and hydrogen.

In some embodiments, the hydrogen-metabolizing chemolithotrophicorganism is capable of metabolizing carbon dioxide and hydrogen via theCalvin-Benson cycle.

In some embodiments, the fermentation or bio-derived product of thebiocatalytic processes described herein comprises a volatile product. By“volatile product,” what is meant is a product having a boiling pointlower than that of water. In some embodiments, the volatile product is agas at the conditions of the fermentation zone. In some embodiments, thevolatile product comprises an alkene, for example butadiene, isoprene,or isobutene.

In some embodiments, the fermentation or bio-derived product of thebiocatalytic processes described herein comprises a single-cell organismor biomass.

In some embodiments, the fermentation or bio-derived product of thebiocatalytic processes described herein comprises a single-cell organismor biomass comprising a poly-hydroxybutyric acid (PHB).

In some embodiments, the fermentation or bio-derived product of thebiocatalytic processes described herein comprises an alkene, for examplebutadiene, isoprene, or isobutene, or an alkene precursor, for example a3-hydroxy-enoic acid, an enol, or a 3-hydroxyacid.

In some embodiments, the fermentation or bio-derived product of thebiocatalytic processes described herein comprises a compound, or a saltthereof, selected from one or more of an amino acid, a hydroxycarboxylicacid, a hydroxylamine, a diamine, a lactam, a carboxylic alcohol, acarboxylic diol, a carboxylic polyol, a carboxylic diamine, or acarboxylic diacid. For example, in some embodiments, the fermentation orbio-derived product comprises a compound, or a salt thereof, selectedfrom one or more of 6-aminohexanoic acid, 7-aminoheptanoic acid,hexamethylenediamine, adipic acid, caprolactam, 1,6-hexanediol, or1,5-pentamethylene diamine.

The present disclosure includes compositions comprising a fermentationor bio-derived product produced by a biocatalytic process as describedherein, as claimed herein, or as shown in any of the Figures. Thepresent disclosure includes compositions comprising an AS, a GS, and anorganism, wherein the organism or an equivalent or engineered equivalentthereof is a methanotroph or a hydrogen-metabolizing or CO-metabolizingchemolithotrophic organism, and wherein the organism is capable ofmixotrophic metabolism of at least one gaseous substrate in the GS andat least one substrate in the AS.

Also described herein are compositions comprising an AS and a GS,wherein the compositions are suitable to biocatalytic processes asdescribed herein. Also described herein are compositions comprising anAS, a GS, and an organism, wherein the compositions are suitable tobiocatalytic processes as described herein. Also described herein arecompositions comprising an AS, a GS, an organism, and at least oneproduct of biocatalytic processes as described herein.

The present disclosure includes systems for producing a fermentation orbio-derived product, comprising: a member suitable for providing an ASor derivative thereof to a fermentation zone; a member suitable forproviding a GS or derivative thereof to a fermentation zone; afermentation zone, the fermentation zone comprising at least oneorganism capable of mixotrophic metabolism of an AS substrate and a GSsubstrate, wherein the fermentation operates at conditions tosimultaneously ferment at least one gaseous substrate in the GS and atleast one substrate present in the AS; one of more fermentation zonecontrol members, suitable for controlling the conditions for fermenting;and a zone for treating the product. In some embodiments, the zone fortreating the product is optional. In some embodiments the zone fortreating the product facilitates a separation step. The AS and GSprovided to such systems may be as described previously herein. The atleast one organism capable of mixotrophic metabolism may be as describedpreviously herein. The fermentation conditions may be as describedpreviously herein.

The present disclosure includes compositions comprising a fermentationor bio-derived product produced by a biocatalytic process as describedherein, as claimed herein, or as shown in any of the Figures. Thepresent disclosure includes compositions comprising an AS comprising (1)at least one polyol such glycerol, carbohydrates, or oligomers ofcarbohydrate, and (2) a carboxylic acid such as acetic acid, lacticacid, succinic acid or butyric acid or derivative, and an organism,wherein the organism or an equivalent or engineered equivalent thereofis capable of metabolizing (1) at least one polyol such glycerol,carbohydrates, or oligomers of carbohydrate, and (2) a carboxylic acidsuch as acetic acid, lactic acid, succinic acid or butyric acid orderivative in the AS.

Also described herein are compositions comprising an AS wherein thecompositions are suitable to biocatalytic processes as described herein.Also described herein are compositions comprising an AS, and anorganism, wherein the compositions are suitable to biocatalyticprocesses as described herein. Also described herein are compositionscomprising an AS, an organism, and at least one product of biocatalyticprocesses as described herein.

The present disclosure includes systems for producing a fermentation orbio-derived product, comprising: a member suitable for providing an ASor derivative comprising (1) at least one polyol such glycerol,carbohydrates, or oligomers of carbohydrate, and (2) a carboxylic acidsuch as acetic acid, lactic acid, succinic acid or butyric acid orderivative thereof to a fermentation zone; a fermentation zone, thefermentation zone comprising at least one organism capable of metabolismof at least one polyol such glycerol, carbohydrates, or oligomers ofcarbohydrate, and (2) a carboxylic acid such as acetic acid, lacticacid, succinic acid or butyric acid, wherein the fermentation operatesat conditions to simultaneously ferment at least one polyol such asglycerol, a carbohydrate, or an oligomer of a carbohydrate, and (2) acarboxylic acid such as acetic acid, lactic acid, succinic acid orbutyric acid; one of more fermentation zone control members, suitablefor controlling the conditions for fermenting; and a zone for treatingthe product. The AS provided to such systems may be as describedpreviously herein. At least one organism capable of simultaneousmetabolism may be as described previously herein. The fermentationconditions may be as described previously herein.

Any patent, publication, or other disclosure material, in whole or inpart, that is said to be incorporated by reference herein isincorporated herein only to the extent that the incorporated materialdoes not conflict with existing definitions, statements, or otherdisclosure material set forth in this disclosure. As such, and to theextent necessary, the disclosure as explicitly set forth hereinsupersedes any conflicting material incorporated herein by reference.Any material, or portion thereof, that is said to be incorporated byreference herein, but which conflicts with existing definitions,statements, or other disclosure material set forth herein will only beincorporated to the extent that no conflict arises between thatincorporated material and the existing disclosure material.

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

EXAMPLES Comparative Example 1A. Isoprene from Aerobic Fermentation ofGlycerol in Thin Stillage

The aqueous thin stillage stream containing lactic acid (16.8 g/L) andglycerol (14.4 g/L) from a corn dry mill bioethanol plant producing 50million gallons of ethanol/year is recovered and fed to an aerobicfermentation utilizing E. coli bacteria and maintained at a pH of 6.5 to7.0 and a temperature of 30° C. Only the glycerol, not the lactic acid,is converted to product. The aerobic fermentation produces 3,500 metrictons/year of isoprene (70% of theoretical yield), and co-produces 5,600metric tons/year of by-product carbon dioxide that is not utilized (seeTable 2).

Example 1B. Isoprene from Aerobic Fermentation of Thin Stillage

The aqueous thin stillage stream of Example 1A is recovered and fed toan aerobic fermentation utilizing C. necator bacteria and maintained ata pH of 6.5 to 7.0 and a temperature of 30° C. The aerobic fermentationferments at least the glycerol and lactic acid from the thin stillagestream to produce 7,200 metric tons/year of isoprene (70% of theoreticalyield), a 110% increase (2.1×) in isoprene production relative toComparative Example 1A, and co-produces 13,500 metric tons/year ofby-product carbon dioxide that is not utilized (see Table 2).

Example 1C. Isoprene from Mixotrophic Aerobic Fermentation of ThinStillage with Hydrogen

The aqueous thin stillage stream of Example 1A is recovered and fed toan aerobic fermentation utilizing C. necator bacteria and maintained ata pH of 6.5 to 7.0 and a temperature of 30° C. The aerobic fermentationferments at least the glycerol and lactic acid from the thin stillagestream. Purchased hydrogen is fed to the aerobic fermentation insufficient quantity to convert approximately 60% of the by-productcarbon dioxide from fermentation of the thin stillage. The aerobicfermentation produces 8,900 metric tons/year of isoprene (70% oftheoretical yield), a 160% increase (2.6×) in isoprene productionrelative to Comparative Example 1A, and co-produces 8,700 metrictons/year of by-product carbon dioxide from the thin stillagefermentation that is not utilized (see Table 2).

Example 1D. Isoprene from Mixotrophic Aerobic Fermentation of ThinStillage and Bioethanol Fermenter Off-Gas Carbon Dioxide with Hydrogen

The aqueous thin stillage stream of Example 1A is recovered and fed to amixotrophic aerobic fermentation utilizing C. necator bacteria andmaintained at a pH of 6.5 to 7.0 and a temperature of 30° C. The aerobicfermentation ferments at least the glycerol and lactic acid from thethin stillage stream. Approximately a 20% portion of the fermenteroff-gas containing carbon dioxide from the corn dry mill bioethanolplant of Example 1A is also recovered and fed to the mixotrophic aerobicfermentation. Purchased hydrogen is also fed to the mixotrophic aerobicfermentation in sufficient quantity to convert approximately 60% of theby-product carbon dioxide from fermentation of the thin stillage and thecarbon dioxide in the 20% portion of bioethanol plant fermenter off-gas.The mixotrophic aerobic fermentation produces 12,800 metric tons/year ofisoprene (70% of theoretical yield), a 270% increase (3.7×) in isopreneproduction relative to Comparative Example 1A, and co-produces 8,700metric tons/year of by-product carbon dioxide from the thin stillagefermentation that is not utilized (see Table 2).

Comparative Example 2A: 7-Aminoheptanoic Acid from Aerobic Fermentationof Glycerol in Thin Stillage

The aqueous thin stillage stream containing lactic acid (16.8 g/L) andglycerol (14.4 g/L) from a corn dry mill bioethanol plant producing 50million gallons of ethanol/year is recovered and fed along with anexcess stoichiometric amount of aqueous ammonia to an aerobicfermentation utilizing E. coli bacteria and maintained at a pH of 6.5 to7.0 and a temperature of 30° C. Only the glycerol, not the lactic acid,is converted to product. The aerobic fermentation produces 5,500 metrictons/year of 7-aminoheptanoic acid (70% of theoretical yield), andco-produces 5,000 metric tons/year of by-product carbon dioxide that isnot utilized (see Table 2).

Example 2B: 7-Aminoheptanoic Acid from Aerobic Fermentation of ThinStillage

The aqueous thin stillage stream of Example 2A is recovered and fedalong with an excess stoichiometric amount of aqueous ammonia to anaerobic fermentation utilizing C. necator bacteria and maintained at apH of 6.5 to 7.0 and a temperature of 30° C. The aerobic fermentationferments at least the glycerol and lactic acid from the thin stillagestream to produce 11,600 metric tons/year of 7-aminoheptanoic acid (70%of theoretical yield), a 110% increase (2.1×) in 7-aminoheptanoic acidproduction relative to Comparative Example 2A, and co-produces 12,000metric tons/year of by-product carbon dioxide that is not utilized (seeTable 2).

Example 2C. 7-Aminoheptanoic Acid from Mixotrophic Aerobic Fermentationof Thin Stillage with Hydrogen

The aqueous thin stillage stream of Example 2A is recovered and fedalong with an excess stoichiometric amount of aqueous ammonia to anaerobic fermentation utilizing C. necator bacteria and maintained at apH of 6.5 to 7.0 and a temperature of 30° C. The aerobic fermentationferments at least the glycerol and lactic acid from the thin stillagestream. Purchased hydrogen is fed to the aerobic fermentation insufficient quantity to convert approximately 60% of the by-productcarbon dioxide from fermentation of the thin stillage. The aerobicfermentation produces 14,000 metric tons/year of 7-aminoheptanoic acid(70% of theoretical yield), a 150% increase (2.5×) in 7-aminoheptanoicacid production relative to Comparative Example 2A, and co-produces7,800 metric tons/year of byproduct carbon dioxide from the thinstillage fermentation that is not utilized (see Table 2).

Example 2D. 7-Aminoheptanoic Acid from Mixotrophic Aerobic Fermentationof Thin Stillage and Bioethanol Fermenter Off-Gas Carbon Dioxide withHydrogen

The aqueous thin stillage stream of Example 2A is recovered and fedalong with an excess stoichiometric amount of aqueous ammonia to amixotrophic aerobic fermentation utilizing C. necator bacteria andmaintained at a pH of 6.5 to 7.0 and a temperature of 30° C. The aerobicfermentation ferments at least the glycerol and lactic acid from thethin stillage stream. Approximately a 20% portion of the fermenteroff-gas containing carbon dioxide from the corn dry mill bioethanolplant of Example 2A is also recovered and fed to the mixotrophic aerobicfermentation. Purchased hydrogen is also fed to the mixotrophic aerobicfermentation in sufficient quantity to convert approximately 60% of thebyproduct carbon dioxide from fermentation of the thin stillage and thecarbon dioxide in the 20% portion of bioethanol plant fermenter off-gas.The mixotrophic aerobic fermentation produces 19,900 metric tons/year of7-aminoheptanoic acid (70% of theoretical yield), a 260% increase (3.6×)in 7-aminoheptanoic acid production relative to Comparative Example 2A,and co-produces 7,800 metric tons/year of by-product carbon dioxide fromthe thin stillage fermentation that is not utilized (see Table 2).

Comparative Example 3A. Biomass from Aerobic Fermentation of Glycerol inThin Stillage

The aqueous thin stillage stream containing lactic acid (16.8 g/L) andglycerol (14.4 g/L) from a corn dry mill bioethanol plant producing 50million gallons of ethanol/year is recovered and fed along with anexcess stoichiometric amount of aqueous ammonia to an aerobicfermentation utilizing E. coli bacteria and maintained at a pH of 6.5 to7.0 and a temperature of 30° C. Only the glycerol, not the lactic acid,is converted to product. The aerobic fermentation produces 5,200 metrictons/year of biomass (25% by wt PHB, 70% of theoretical yield), andco-produces 7,000 metric tons/year of by-product carbon dioxide that isnot utilized (see Table 2).

Example 3B. Biomass from Aerobic Fermentation of Thin Stillage

The aqueous thin stillage stream of Example 3A is recovered and fedalong with an excess stoichiometric amount of aqueous ammonia to anaerobic fermentation utilizing C. necator bacteria and maintained at apH of 6.5 to 7.0 and a temperature of 30° C. The aerobic fermentationferments at least the glycerol and lactic acid from the thin stillagestream to produce 11,900 metric tons/year of biomass (25% by wt PHB, 70%of theoretical yield), a 130% increase (2.3×) in biomass (25% by wt PHB)production relative to Comparative Example 3A, and co-produces 14,600metric tons/year of by-product carbon dioxide that is not utilized (seeTable 2).

Example 3C. Biomass from Mixotrophic Aerobic Fermentation of ThinStillage with Hydrogen

The aqueous thin stillage stream of Example 3A is recovered and fedalong with an excess stoichiometric amount of aqueous ammonia to anaerobic fermentation utilizing C. necator bacteria and is maintained ata pH of 6.5 to 7.0 and a temperature of 30° C. The aerobic fermentationferments at least the glycerol and lactic acid from the thin stillagestream. Purchased hydrogen is fed to the aerobic fermentation insufficient quantity to convert approximately 60% of the by-productcarbon dioxide from fermentation of the thin stillage. The aerobicfermentation produces 15,200 metric tons/year of biomass (25% by wt PHB,70% of theoretical yield), a 190% increase (2.9×) in biomass (25% by wtPHB) production relative to Comparative Example 3A, and co-produces9,400 metric tons/year of by-product carbon dioxide from the thinstillage fermentation that is not utilized (see Table 2).

Example 3D. Biomass from Mixotrophic Aerobic Fermentation of ThinStillage and Bioethanol Fermenter Off-Gas Carbon Dioxide with Hydrogen

The aqueous thin stillage stream of Example 3A is recovered and fedalong with an excess stoichiometric amount of aqueous ammonia to amixotrophic aerobic fermentation utilizing C. necator bacteria andmaintained at a pH of 6.5 to 7.0 and a temperature of 30° C. The aerobicfermentation ferments at least the glycerol and lactic acid from thethin stillage stream. Approximately a 20% portion of the fermenteroff-gas containing carbon dioxide from the corn dry mill bioethanolplant of Example 3A is also recovered and fed to the mixotrophic aerobicfermentation. Purchased hydrogen is also fed to the mixotrophic aerobicfermentation in sufficient quantity to convert approximately 60% of theby-product carbon dioxide from fermentation of the thin stillage and thecarbon dioxide in the 20% portion of bioethanol plant fermenter off-gas.The mixotrophic aerobic fermentation produces 21,900 metric tons/year ofbiomass (25% by wt PHB, 70% of theoretical yield), a 320% increase(4.2×) in biomass (25% by wt PHB) production relative to ComparativeExample 3A, and co-produces 9,400 metric tons/year of by-product carbondioxide from the thin stillage fermentation that is not utilized (seeTable 2).

TABLE 2 Exemplary aerobic fermentation products and production ratesversus comparative production rates for Examples 1A to 3D in a 50million gal/yr corn dry mill bioethanol plant. Annual Production Rate,Annual Other Aerobic (metric Production Example Relevant Feed feedfermentation tons Rate vs. No. FIG. No. streams streams productproduct/yr) Comparative Comparative 3A thin — isoprene  3,500   1× 1Astillage (only glycerol converts) 1B 3A thin — isoprene  7,200 2.1×stillage (110% (glycerol increase) and lactic acid converts) 1C 3B thinH₂ isoprene  8,900 2.6× stillage (160% (glycerol increase) and lacticacid converts) 1D 3C thin H₂ isoprene 12,800 3.7× stillage (270%(glycerol increase) and lactic acid converts) + 20% of fermenter off-gasComparative 3A thin NH₃(aq) 7-aminoheptanoic  5,500   1× 2A stillageacid (only glycerol converts) 2B 3A thin NH₃(aq) 7-aminoheptanoic 11,6002.1× stillage acid (110% increase) 2C 3B thin NH₃(aq), 7-aminoheptanoic14,000 2.5× stillage H₂ acid (150% increase) 2D 3C thin NH₃(aq),7-aminoheptanoic 19,900 3.6× stillage + H₂ acid (260% 20% of increase)fermenter off-gas Comparative 3A thin NH₃(aq) biomass  5,200   1× 3Astillage (25 wt % PHB) (only glycerol converts) 3B 3A thin NH₃(aq)biomass 11,900 2.3× stillage (25 wt % PHB) (130% increase) 3C 3B thinNH₃(aq), biomass 15,200 2.9× stillage H₂ (25 wt % PHB) (190% increase)3D 3C thin NH₃(aq), biomass 21,900 4.2× stillage + H₂ (25 wt % PHB)(320% 20% of increase) fermenter off-gas

What is claimed is:
 1. A biocatalytic process comprising: providing anaqueous stream, and/or derivative thereof, comprising at least onefermentable substrate to a fermentation zone; and providing a gaseousstream to the fermentation zone, wherein the gaseous stream comprises atleast one substrate selected from CO₂, H₂, CO₂/H₂, methane, and CO,wherein the aqueous stream and gaseous stream are optionally contactedand/or mixed in the fermentation zone; the fermentation zone comprisingat least one organism capable of metabolizing the aqueous stream and thegaseous stream, wherein the fermentation operates at conditions tomixotrophically metabolize at least one gaseous substrate in the gaseousstream and at least one substrate in the aqueous stream; and forming atleast one product via the fermentation.
 2. The process of claim 1,wherein the at least one organism is a naturally occurring organism, ora derivative thereof.
 3. The process of claim 2, wherein the organism oran equivalent or engineered equivalent thereof is a methanotroph, ahydrogen-metabolizing chemolithotrophic organism, or a CO-metabolizingchemolithotrophic organism.
 4. The process of claim 3, wherein theorganism is Cupriavidus necator or Clostridium sp., or an equivalent orengineered equivalent thereof.
 5. The process of claim 4, wherein theorganism is Cupriavidus necator, or an equivalent or engineeredequivalent thereof.
 6. The process of claim 1, wherein the gaseousstream is or is derived from natural gas, which is combusted in at leastone combined heat and power (CHP) unit to generate power.
 7. The processof claim 6, wherein heat from the combined heat and power unit generatessteam that is used to drive a turbo generator for generating electricpower.
 8. The process of claim 1, wherein the gaseous stream is or isderived from natural gas, and at least a portion of the gaseous streamis provided to a gas combustion turbo-generator to generate power. 9.The process of claim 1, wherein the gaseous stream is or is derived fromsyngas, and at least a portion of the gaseous stream drives anon-combusting turbo-generator to generate power.
 10. The process ofclaim 1, wherein the gaseous stream is or is derived from natural gas,such that at least a portion of the gaseous stream is provided to asteam methane reformation for producing syngas, and at least a portionof the produced syngas is provided to a gas generator to generate power.11. The process of any one of claims 6-10, wherein the power generationprovides for H₂ production via water electrolysis, thereby producing H₂and O₂, wherein said H₂ is used in the fermentation.
 12. The process ofclaim 11, wherein the O₂ is used in the fermentation.
 13. The process ofclaim 12, wherein the generated electric power is: integrated orexported; used in a bio-ethanol production process; provides for H₂production via water electrolysis, thereby producing H₂ for use in thefermentation; or a combination thereof.
 14. The process of claim 1,wherein the gaseous stream comprises H₂ and optionally comprises CO₂,wherein the H₂ and optionally CO₂ is obtained from a steam methanereformation, optionally further comprising a water gas shift process.15. A biocatalytic process comprising: providing an aqueous stream,and/or derivative thereof, comprising at least one fermentable substrateto a fermentation zone; and providing a gaseous stream to thefermentation zone, wherein the gaseous stream comprises at least H₂,wherein the aqueous stream and gaseous stream are optionally contactedand/or mixed in the fermentation zone; the fermentation zone comprisingat least one hydrogen-metabolizing chemolithotropic organism capable ofmetabolizing the aqueous stream and the gaseous stream, wherein thefermentation operates at conditions to mixotrophically metabolize atleast H₂ in the gaseous stream and/or at least one substrate in theaqueous stream; and forming at least one product via the fermentation.16. The process of claim 15, wherein said hydrogen chemolithotrophicorganism is Cupriavidus necator or a derivative thereof.
 17. The processof claim 15, wherein the aqueous stream comprises glycerol and lacticacid.
 18. The process of claim 17, wherein said fermentation operates atconditions to mixotrophically metabolize at least H₂ in the gaseousstream and glycerol and lactic acid in the aqueous stream.
 19. Theprocess of any one of the preceding claims, wherein the aqueous streamcomprises at least one of a spent fermentation stream, stillage from abio-ethanol production process, thin stillage stream from a bio-ethanolproduction process, whole stillage stream from a bio-ethanol productionprocess, and an aqueous stream comprising one or more of glycerol,carbohydrate, oligomers of carbohydrates, protein, carboxylic acid,acetic acid, and lactic acid.
 20. The process of any one of thepreceding claims, further comprising: removing a fermentation brothbleed stream from the fermentation zone; treating the fermentation brothbleed stream to remove biomass and produce a biomass-free broth; andrecycling the biomass-free broth to a fermentation step of thebiocatalytic process.
 21. The process of any one of the precedingclaims, wherein in the fermentation zone the gaseous stream substratehas a CO₂:H₂ molar ratio ranging from 0 to 0.35 mol CO₂/mol H₂.
 22. Theprocess of any one of the preceding claims, wherein the conditions tomixotrophically metabolize at least one gaseous substrate in the gaseousstream and at least one substrate present in the aqueous stream are a pHranging from 6 to 8, a temperature ranging from 30° C. to 40° C., and apressure of above 1 atm absolute.
 23. The process of claim 22, whereinthe pressure ranges from 1.5 to 5 atm absolute.
 24. The process of claim22, wherein the pressure is above 2.5 atm absolute.
 25. The process ofany one of the preceding claims, wherein the at least one organismcomprises at least one of (1) a genetic alteration, (2) a chemicalalteration, and (3) a non-naturally occurring alteration.
 26. Abiocatalytic process comprising: providing an aqueous stream to afermentation zone, wherein said aqueous stream comprises (1) at leastone polyol such glycerol, carbohydrates, or oligomers of carbohydrate,and (2) a carboxylic acid such as acetic acid, lactic acid, succinicacid or butyric acid; the fermentation zone comprising at least onebacterium or genetically-modified bacterium capable of metabolizing atleast one of the polyols and at least one of the carboxylic acids in theaqueous stream, wherein the fermentation operates at conditions tometabolize at least one of the polyols and at least one of thecarboxylic acids in the aqueous stream; and forming at least onebio-derived product.
 27. The biocatalytic process according to claim 26,wherein said aqueous stream comprises glycerol and lactic acid and saidfermentation zone comprises at least one bacteria orgenetically-modified bacteria capable of metabolizing said glycerol andsaid lactic acid, and wherein the fermentation operates at conditions tometabolize said glycerol and lactic acid in the aqueous stream.
 28. Thebiocatalytic process according to claim 26 or 27, wherein said at leastone bacterium or genetically-modified bacterium is Cupriavidus necator.29. The process of any one of the preceding claims, wherein thefermentation or bio-derived product comprises a volatile product. 30.The process of claim 29, wherein the volatile product is a gas at theconditions of the fermentation zone.
 31. The process of claim 30,wherein the volatile product comprises at least one alkene chosen frombutadiene, isoprene, and isobutene or derivative thereof.
 32. Theprocess of any one of the preceding claims, wherein the fermentation orbio-derived product comprises at least one alkene precursor chosen from3-hydroxy-enoic acid, an enol, and a 3-hydroxyacid or derivativethereof.
 33. The process of any one of the preceding claims, wherein thefermentation or bio-derived product comprises one or more compounds, orsalts thereof, selected from an amino acid, a hydroxycarboxylic acid, ahydroxylamine, a diamine, a lactam, a carboxylic alcohol, a carboxylicdiol, a carboxylic polyol, a carboxylic diamine, or a carboxylic diacid.34. The process of any one of the preceding claims, wherein thefermentation or bio-derived product comprises one or more compounds, orsalts thereof, selected from 6-aminohexanoic acid, 7-aminoheptanoicacid, hexamethylenediamine, adipic acid, caprolactam, 1,6-hexanediol, or1,5-pentamethylene diamine.
 35. The process of any one of the precedingclaims, wherein the fermentation or bio-derived product comprisesbiomass.
 36. The process of claim 35, wherein the biomass comprises apoly-hydroxybutyric acid, or a salt thereof.
 37. The process of any oneof the preceding claims, wherein the aqueous stream is obtained from amilled ethanol production process.
 38. A composition comprising afermentation or bio-derived product produced by at least one processaccording to any one of the preceding claims, or as described in any ofthe Figures.
 39. A composition comprising an aqueous stream, a gaseousstream, and an organism, wherein the organism or an equivalent orengineered equivalent thereof is a methanotroph or ahydrogen-metabolizing or CO-metabolizing chemolithotrophic organism, andwherein the organism is capable of mixotrophic metabolism of at leastone gaseous substrate in the gaseous stream and at least one substratein the aqueous stream.
 40. A composition comprising an aqueous streamand a gaseous stream, wherein said composition can be used as afeedstock for a biocatalytic process according to claim
 1. 41. Acomposition comprising an aqueous stream, a gaseous stream, and anorganism, wherein said composition can be used as a feedstock for abiocatalytic process according to claim
 1. 42. A composition comprisingan aqueous stream, a gaseous stream, an organism, and at least oneproduct of a biocatalytic process according to claim
 1. 43. A system forproducing a fermentation or bio-derived product, comprising: a member toprovide an aqueous stream or derivative thereof to a fermentation zone;a member to provide a gaseous stream or derivative thereof to afermentation zone; a fermentation zone, the fermentation zone comprisingat least one organism capable of mixotrophic metabolism of an aqueousstream substrate and a gaseous stream substrate, wherein thefermentation operates at conditions to simultaneously ferment at leastone gaseous substrate in the gaseous stream and at least one substratepresent in the aqueous stream; one of more fermentation zone controlmembers, to control the conditions for fermenting; and a zone fortreating the product.
 44. A biocatalytic process for producing aproduct, comprising: providing an aqueous stream, and/or derivativethereof, having at least one fermentable substrate to a fermentationzone; providing a gaseous stream comprising at least one of CO₂, H₂,CO₂/H₂, methane, and CO to the fermentation zone, the fermentation zonecomprising at least one organism capable of metabolizing at least onesubstance in the aqueous stream; wherein the aqueous stream comprises(1) at least one glycerol, carbohydrates, or oligomers of carbohydrate,and (2) a carboxylic acid; and wherein the organism is capable ofmetabolizing at least one substance in the gaseous stream.
 45. Thebiocatalytic process of claim 44, wherein the carboxylic acid is chosenfrom a fatty acid, lactic acid, and acetic acid or derivatives thereof.46. The process of any one of the preceding claims, wherein the aqueousstream is from a bioethanol process.